CN109957046B - Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator - Google Patents

Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator Download PDF

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CN109957046B
CN109957046B CN201711415551.4A CN201711415551A CN109957046B CN 109957046 B CN109957046 B CN 109957046B CN 201711415551 A CN201711415551 A CN 201711415551A CN 109957046 B CN109957046 B CN 109957046B
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ester photoinitiator
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钱晓春
胡春青
于培培
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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Abstract

The invention provides a fluorine-containing fluorene oxime ester photoinitiator, a photocuring composition containing the same and application of the composition. The photoinitiator has a structure shown in a general formula (I). In the fluorine-containing fluorene oxime ester photoinitiator provided by the application, a polymerizable group is introduced into the 9-position of a fluorene structure, so that the formed photoinitiator can be polymerized with a base material, and the photoinitiator has the advantage of difficult migration. Meanwhile, due to the introduction of the fluorine-containing group, the photoinitiator provided by the application also has the advantage of high initiation efficiency. In addition, the structural specificity enables the photoinitiator to have the advantages of good surface drying performance, good surface curing effect and the like. On the basis, the photoinitiator has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like, and has wide application prospect.

Description

Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a fluorine-containing fluorene oxime ester photoinitiator, a photocuring composition containing the same and application of the composition.
Background
Compared with the traditional kinescope monitor, the liquid crystal display device has the advantages of low energy consumption, small volume and no radiation, but still has the defects of small visible angle, trailing image, poor brightness and contrast. In recent years, with the increasing living standard of people, people have made higher demands on liquid crystal display devices, and demands for large size, high luminance, high contrast, wide viewing angle, and the like are mentioned, which makes higher demands on materials used in the manufacture of liquid crystal displays.
Color and black photoresist and photo spacers are important components of a liquid crystal flat panel display, and are essential materials for realizing large size and high resolution of advanced flat panel display, and a high-sensitivity oxime ester initiator is an important component of a photoresist and spacer formula.
Disclosure of Invention
The invention mainly aims to provide a fluorine-containing fluorene oxime ester photoinitiator, a photocuring composition containing the same and application of the composition, so as to solve the problems of poor surface dryness and easy migration of the existing oxime ester photoinitiator.
In order to achieve the purpose, the invention provides a fluorine-containing fluorenyloxime ester photoinitiator, which has a structure shown in a general formula (I):
Figure BDA0001520771200000011
wherein n represents an integer of 1 to 4; m represents an integer of 1 to 4;
n number of R1Each independently selected from-G- (M')qHydrogen, nitro, halogen, or
Figure BDA0001520771200000021
m represents an integer of 1 to 4; wherein G is selected from heteroatom or carbonyl, heteroatom is O, N or S, M' is selected from C1～C20Straight or branched alkyl of (2), C3～C8Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (2)、C6～C20Aryl of (C)1～C10Alkyl, nitro substituted C6～C20Aryl, cyano-substituted C6～C20Aryl radical, C4～C20Heteroaryl, nitro substituted C of6～C20Heteroaryl or cyano-substituted C6～C20Heteroaryl, or one or more carbon atoms of M' is substituted with a heteroatom, q is 1 or 2;
R2and R2' each is independently selected from polymerizable groups;
z and Z' each independently represent a null or a carbonyl group;
m R3And m' R5Each independently selected from fluorine, linear or branched alkyl substituted by one or more fluorine, linear or branched alkoxy substituted by one or more fluorine;
R4and R6Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C1～C10Alkyl radical, C1～C10Alkyl-substituted C of3～C8Cycloalkyl radical, C6～C20Aryl of (C)4～C20Heteroaryl or C of2～C20Alkenyl groups of (a).
By applying the technical scheme of the invention, polymerizable groups are introduced into the 9-position of the fluorene structure in the fluorine-containing fluorene oxime ester photoinitiator provided by the application, so that the formed photoinitiator can be polymerized with a base material, and the photoinitiator has the advantage of difficult migration. Meanwhile, due to the introduction of the fluorine-containing group, the photoinitiator provided by the application also has the advantage of high initiation efficiency. In addition, the structural specificity enables the photoinitiator to have the advantages of good surface drying performance, good surface curing effect and the like. On the basis, the photoinitiator has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like, and has wide application prospect.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the prior oxime ester photoinitiators have the problems of poor surface drying property and easy migration. In order to solve the technical problems, the invention provides a fluorine-containing fluorene oxime ester photoinitiator, which has a structure shown in a general formula (I):
Figure BDA0001520771200000031
wherein n represents an integer of 1 to 4; m represents an integer of 1 to 4;
n number of R1Each independently selected from-G- (M')qHydrogen, nitro, halogen, or
Figure BDA0001520771200000032
m' represents an integer of 1 to 4; wherein G includes but is not limited to a heteroatom or a carbonyl group, the heteroatom is O, N or S, M' includes but is not limited to C1～C20Straight or branched alkyl of (2), C3～C8Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)6～C20Aryl of (C)1～C10Alkyl, nitro substituted C6～C20Aryl, cyano-substituted C6～C20Aryl radical, C4～C20Heteroaryl, nitro substituted C of6～C20Heteroaryl or cyano-substituted C6～C20Heteroaryl, or one or more carbon atoms of M' is substituted with a heteroatom, q is 1 or 2;
R2and R2' each is independently selected from polymerizable groups; z and Z' each independently represent a null or a carbonyl group; m R3And m's of R5Each independently selected from fluorine, linear or branched alkyl substituted by one or more fluorine, linear or branched alkoxy substituted by one or more fluorineA group; r4And R6Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C1～C10Alkyl radical, C1～C10Alkyl-substituted C of3～C8Cycloalkyl radical, C6～C20Aryl of (C)4～C20Heteroaryl or C of2～C20Alkenyl groups of (a).
In the fluorine-containing fluorene oxime ester photoinitiator provided by the application, a polymerizable group is introduced into the 9-position of a fluorene structure, so that the formed photoinitiator can be polymerized with a base material, and the photoinitiator has the advantage of difficult migration. Meanwhile, due to the introduction of the fluorine-containing group, the photoinitiator provided by the application also has the advantage of high initiation efficiency. In addition, the structural specificity enables the photoinitiator to have the advantages of good surface drying performance, good surface curing effect and the like. On the basis, the photoinitiator has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like, and has wide application prospect.
In order to further improve the structural stability of the fluorine-containing fluorenyloxime ester photoinitiator, M' preferably includes but is not limited to C1～C10Straight or branched alkyl of (2), C3～C6Cycloalkyl of, C3～C6Cycloalkyl-substituted C of1～C5Alkyl of (C)6～C10Aryl of (C)1～C5Alkyl, nitro substituted C6～C10Aryl, cyano-substituted C6～C10Aryl radical, C4～C10Heteroaryl, nitro substituted C of6～C10Heteroaryl or cyano-substituted C6～C10A heteroaryl group.
In order to further reduce the mobility of the fluorine-containing fluorenyloxime ester photoinitiator, R is preferably2And R2' are each independently selected from polymerizable groups containing a double bond or an epoxy group.
At one endIn a preferred embodiment, R2And R2' each is independently selected from C2～C12Or R is2And R2' one or more of-CH2Each of which may be independently substituted by-O-,
Figure BDA0001520771200000041
substituted;
preferably, R2And R2' each is independently selected from C3～C8Or R is2In one or more-CH2Each of which may be independently substituted by-O-,
Figure BDA0001520771200000042
and (4) substituting.
In a preferred embodiment, R2And R2' each is independently selected from the group consisting of ethylene oxide substituted C1～C10Alkyl or propylene oxide substituted C1～C10Alkyl, or R2And R2' middle C1～C10One or more-CH's in alkyl2Each independently of the others by-O-),
Figure BDA0001520771200000043
or-O-CH2-CH(OH)-CH2-O-substitution.
In a preferred embodiment, R2And R2' C independently selected from ethylene oxide or cyclopropyl alkyl as end capping group1～C8Or R is2And R2' middle C1～C8One or more-CH in alkyl group of (2)2Each independently of the others by-O-),
Figure BDA0001520771200000044
Figure BDA0001520771200000045
or-O-CH2-CH(OH)-CH2O-or H in an ethylene oxide or propylene oxide radical may be substituted by C1～C4Is substituted with an alkyl group.
Preferably, m R3And m's of R5Are respectively and independently selected from F,
Figure BDA0001520771200000046
Figure BDA0001520771200000047
The above-mentioned groups are selected as R3And R5Is favorable for further improving the initiation efficiency of the photoinitiator.
Preferably, R4And R6Are each independently selected from C1～C6Straight or branched alkyl of (2), C3～C10Cycloalkyl of, C3～C6Cycloalkyl-substituted C1～C8Alkyl radical, C1～C8Alkyl substituted C3～C6Cycloalkyl or C6～C12Aryl group of (1).
More preferably, R4And R6Each independently selected from phenyl and C1～C4Straight or branched alkyl of (2), C3～C8Cycloalkyl or C3～C6Cycloalkyl-substituted C1～C4An alkyl group.
More preferably, the fluorine-containing fluorenyloxime ester photoinitiator is selected from
Figure BDA0001520771200000051
Figure BDA0001520771200000061
Figure BDA0001520771200000071
Figure BDA0001520771200000081
Figure BDA0001520771200000091
Figure BDA0001520771200000101
Figure BDA0001520771200000111
Figure BDA0001520771200000112
One or more of the group consisting of.
According to another aspect of the present invention, the present invention also provides a preparation method of the fluorine-containing fluorenyloxime ester photoinitiator represented by the general formula (I), which comprises the following steps:
(1) preparation of intermediate a
Under the catalytic action of aluminum trichloride or zinc chloride, carrying out Friedel-crafts acylation reaction on the raw material a and the raw material b in an organic solvent to obtain an intermediate a; the synthetic route is as follows:
Figure BDA0001520771200000113
a is empty or methylene.
(2) Preparation of intermediate b
When the intermediate a is subjected to oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate, A is empty to generate an intermediate b, and the synthetic route is as follows:
Figure BDA0001520771200000121
when the intermediate a and nitrite are subjected to oximation reaction at normal temperature in the presence of concentrated hydrochloric acid, A is methylene to generate an intermediate b, and the synthetic route is as follows:
Figure BDA0001520771200000122
(3) preparation of the product
Intermediate b with acid anhydride
Figure BDA0001520771200000123
Or acyl chloride compounds
Figure BDA0001520771200000124
Carrying out esterification reaction to obtain a target product, wherein the synthetic route is as follows:
Figure BDA0001520771200000125
and Z is empty or carbon based.
The starting materials used in the above synthesis are all known compounds and can be obtained commercially or conveniently by known synthetic methods, wherein the starting material a can be obtained according to the synthetic method disclosed in chinese patent application No. 201710274018.4. The synthesis process sequentially comprises a Friedel-crafts acylation reaction, an oximation reaction and an esterification reaction, which are all conventional reaction types in the field of organic chemical synthesis. Specific reaction conditions are readily determined by one skilled in the art after a clear reaction scheme.
The reaction temperature in the step (1) is usually-10 to 30 ℃. The type of the organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and is preferably one or more selected from the group consisting of dichloromethane, dichloroethane, benzene, toluene and xylene.
In the step (2), the preparation of the intermediate b is carried out in a solvent system, and the kind of the solvent used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected. When Z is empty, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction was carried out under heating under reflux. When Z is a carbonyl group, the solvent used includes, but is not limited to, one or more of the group consisting of dichloromethane, benzene, toluene, and tetrahydrofuran, the nitrite includes, but is not limited to, one or more of the group consisting of ethyl nitrite, isoamyl nitrite, and isooctyl nitrite, and the nitrite includes, but is not limited to, sodium nitrite and/or potassium nitrite.
In the step (3), the esterification reaction is carried out in an organic solvent, and the kind of the solvent is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected, and one or more kinds of the group consisting of dichloromethane, dichloroethane, benzene, toluene and xylene are preferable.
According to still another aspect of the present invention, the present invention also provides a photocurable composition, which comprises a photoinitiator, wherein the photoinitiator comprises a fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I).
In the fluorine-containing fluorene oxime ester photoinitiator provided by the application, a polymerizable group is introduced into the 9-position of a fluorene structure, so that the formed photoinitiator can be polymerized with a base material, and the photoinitiator has the advantage of difficult migration. Meanwhile, due to the introduction of the fluorine-containing group, the photoinitiator provided by the application also has the advantage of high initiation efficiency. In addition, the structural specificity enables the photoinitiator to have the advantages of good surface drying performance, good surface curing effect and the like. On the basis, the photoinitiator has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like. The photocuring composition containing the fluorine-containing fluorene oxime ester photoinitiator also has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like.
According to another aspect of the invention, the invention also provides application of the fluorine-containing fluorenyloxime ester photoinitiator shown in the general formula (I) in the field of photocuring.
In the fluorine-containing fluorene oxime ester photoinitiator provided by the application, a polymerizable group is introduced into the 9-position of a fluorene structure, so that the formed photoinitiator can be polymerized with a base material, and the photoinitiator has the advantage of difficult migration. Meanwhile, due to the introduction of the fluorine-containing group, the photoinitiator provided by the application also has the advantage of high initiation efficiency. In addition, the structural specificity enables the photoinitiator to have the advantages of good surface drying performance, good surface curing effect and the like. On the basis, the photoinitiator has the advantages of difficult migration, high initiation efficiency, good surface drying performance, good surface curing effect and the like, and has wide application prospect.
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
(1) Synthesis of intermediate 1a
A500 mL four-necked flask was charged with 66.1g of intermediate 1a, 27.0g of aluminum trichloride and 100mL of methylene chloride, and the temperature of the starting material in the four-necked flask was lowered to 0 ℃ by using an ice water bath. Then, a mixed solution of 57.0g of the raw material 1b and 50mL of methylene chloride was added dropwise to the above raw materials under stirring, and the temperature of the reaction system was controlled to 10 ℃ or lower, and the addition was completed over 2 hours. After the dropwise addition, stirring is continued for 2 hours, and the liquid phase tracking reaction is carried out until the reaction is completed. The reaction mixture was slowly poured into dilute hydrochloric acid prepared from 400g of ice water and 50mL of concentrated hydrochloric acid (37%) with stirring, and then poured into a separatory funnel, the lower dichloromethane layer was separated, and the aqueous layer was further washed with 50mL of dichloromethane, and the dichloromethane layers were combined. The dichloromethane layer was washed with 5 wt% aqueous sodium bicarbonate (150 mL each for 3 times), then washed with water until the pH was neutral, dried over 80g anhydrous magnesium sulfate, filtered, and the dichloromethane product solution was rotary evaporated, recrystallized from methanol as a solvent, and then dried in an oven at 80 ℃ for 2h to give 97.2g of intermediate 1a in 84 wt% yield and 98 wt% purity. The synthetic route is as follows:
Figure BDA0001520771200000141
intermediate 1a was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：1.2885-1.3307(8H，m)，1.8654-1.9975(8H,m)，2.3506(3H，s)，3.8098(2H，s)，4.9657-5.0342(4H，m)，5.6786-5.7153(2H，t)，6.1976(1H，s)，6.4672-6.8400(3H,m),7.2813-7.9503(7H，m)。
MS(m/z)：579(M+1)+。
(2) synthesis of intermediate 1b
57.9g of intermediate 1a, 7.0g of hydroxylamine hydrochloride, 8.2g of sodium acetate, 100mL of ethanol and 50mL of water were added to a 500mL four-necked flask, the reaction was stopped after heating, refluxing and stirring at 85 ℃ for 5 hours, the mixture was poured into a 1000mL large beaker, 500mL of water was added thereto and stirred, 100mL of dichloromethane was used for extraction, 30g of anhydrous MgSO (MgSO) was added to the extract4Drying, vacuum filtering, rotary evaporating the filtrate under reduced pressure to remove solvent, rotating the bottle to obtain oily viscous substance, pouring the viscous substance into 100mL petroleum ether, stirring, vacuum filtering to obtain white powdery solid, oven drying at 70 deg.C for 5 hr to obtain intermediate 1b 43.7g, yield 72 wt%, purity 98 wt%, MS (M/z):608(M +1)+. The synthetic route is as follows:
Figure BDA0001520771200000142
(3) synthesis of Compound 1
Adding 30.4g of intermediate 1b and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 5g of propionyl chloride, continuing stirring for 2h after about 30min of dropwise addition is finished, and then adding 5% NaHCO3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 100mL water for 2 times, and washing with 20g anhydrous MgSO4Drying, filtering, rotary evaporating solvent to obtain viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain compound 1 (27.2 g), with yield of 82% and purity of 99%. The synthetic route is as follows:
Figure BDA0001520771200000151
the structure of compound 1 was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：0.9869-1.0045(3H，t)，1.2895-1.3347(8H,m)，1.8678-1.9668(8H，m)，2.2678-2.3567(5H，m)，4.9678-5.0546(4H，m)，5.6695-5.7206(2H，m)，6.1996(1H，s)，6.7846-8.0331(10H，m)。
MS(m/z)：664(M+1)+。
example 2
(1) Synthesis of intermediate 2a
A500 mL four-necked flask was charged with 72.5g of intermediate 2a, 27.0g of aluminum trichloride, and 100mL of methylene chloride, and the temperature of the starting material in the four-necked flask was lowered to 0 ℃ by using an ice water bath. Then, a mixed solution of 54.5g of the starting material 2b and 50mL of methylene chloride was added dropwise to the above starting material under stirring, and the temperature of the reaction system was controlled to 10 ℃ or lower, and the dropwise addition was completed over 2 hours. After the dropwise addition, stirring is continued for 2 hours, and the liquid phase tracking reaction is carried out until the reaction is completed. Then, the reaction system was slowly poured into dilute hydrochloric acid prepared from 400g of ice water and 50mL of concentrated hydrochloric acid (37%) while stirring, and then poured into a separatory funnel, the lower dichloromethane layer was separated, the aqueous layer was further washed with 50mL of dichloromethane, the dichloromethane layers were combined, the dichloromethane layer was washed with 5 wt% aqueous sodium bicarbonate (150 mL each time, 3 times in total), the dichloromethane layer was washed with water until the pH became neutral, the dichloromethane layer was dried with 80g of anhydrous magnesium sulfate, the dichloromethane product solution was filtered, rotary-distilled, recrystallized with methanol as a solvent, and then oven-dried at 80 ℃ for 2 hours to obtain 101.8g of intermediate 2a, yield 85 wt%, purity 98 wt%. The synthetic route is as follows:
Figure BDA0001520771200000152
intermediate 2a was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：2.1489-2.1673(4H，t)，2.3507(3H，s)，4.1043-4.1554(4H，t)，5.7986-6.0521(4H，m)，6.4207-6.4332(2H，d)，7.1105-7.8023(10H，m)。
MS(m/z)：599(M+1)+。
(2) synthesis of intermediate 2b
59.8g of intermediate 2a, 10.0g of 37 wt% hydrochloric acid, 11.8g of isoamyl nitrite, and 100mL of tetrahydrofuran were put into a 250mL four-necked flask, and stirred at room temperature for 5 hours to stop the reaction. Pouring the material into a 1000mL big beaker, adding 500mL water, stirring, extracting with 100mL dichloromethane, adding the extract into the solution30g of anhydrous MgSO4Drying, suction filtering, removing the solvent from the filtrate by rotary evaporation under reduced pressure, obtaining oily sticky matter in a rotary bottle, pouring the sticky matter into 100mL petroleum ether, stirring, separating out, suction filtering to obtain white powdery solid, drying at 70 ℃ for 5h to obtain an intermediate 2b44.8g, the yield is 75%, the purity is 98%, and MS (m/z): 614(M +1)+. The synthetic route is as follows:
Figure BDA0001520771200000161
(3) synthesis of Compound 2
30.7g of intermediate 2b and 100mL of dichloromethane are added into a 250mL four-neck flask, stirred at room temperature for 5min, then 6.5g of propionic anhydride is added dropwise, stirring is continued for 2h after about 30min of dropwise addition is finished, and then 5% NaHCO is added3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO4Drying, filtering, evaporating solvent to obtain viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain 28.5g product with yield of 85% and purity of 99%.
The synthetic route is as follows:
Figure BDA0001520771200000162
the structure of compound 2 was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：1.0004-1.1049(3H，t)，2.1497-2.2732(6H,m)，4.1003-4.1666(4H,t)，5.8006-6.1056(4H，m)，6.4275-6.4365(2H，d)，7.2809-8.0603(7H，m)。MS(m/z)：670(M+1)+。
example 3
Referring to the methods of examples 1 and 2, compounds 3 to 13 having the structures shown in table 1 were prepared from the respective starting materials.
TABLE 1
Figure BDA0001520771200000171
Figure BDA0001520771200000181
Figure BDA0001520771200000191
Evaluation of photoinitiator Properties
The application performances of the photoinitiator shown in the formula (I) of the invention, such as curing speed, migration, surface dryness and the like, are evaluated by preparing a representative photocurable resin composition, and the specific steps are as follows:
(1) a photocurable resin composition (parts by weight) having the following composition was prepared, as shown in Table 2.
TABLE 2
Figure BDA0001520771200000192
Figure BDA0001520771200000201
Wherein, in table 1 a: 1, 6-hexanediol diacrylate.
Acrylate copolymer [ benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv:10000) ].
C1: compound 1, C2: compound 2, C3: compound 4, C4: compound 7, C5: compound 11, C6: compound 12.
C7 is
Figure BDA0001520771200000202
C8 is
Figure BDA0001520771200000203
C9 is
Figure BDA0001520771200000204
C10 is
Figure BDA0001520771200000205
D1 is butanone (solvent).
(2) And (4) curing speed.
Stirring the composition under a yellow light, taking the composition, forming a film on a PET template by using roll coating, and drying at 90 ℃ for 2min to obtain a coating film with the dry film thickness of 2 mu m. Then, the coating film was cooled to room temperature, and subjected to a high-pressure mercury lamp (exposure machine type: RW-UV70201, single exposure of 50 mJ/cm)2) And irradiating the film to expose the film and cure the film to form a film.
The number of times of the belt-like exposure of the coating film cured into a cured film was evaluated, and the larger the number of times, the less desirable the curing speed was.
(3) Mobility.
Cutting the solidified film into pieces to serve as samples, weighing 0.5g of the solidified film sample, placing the solidified film sample in a 50mL beaker, adding 4.5mL of methanol, ultrasonically dissolving the solidified film sample for 30min by utilizing ultrasonic waves, transferring the obtained solution into a 10mL volumetric flask, continuously washing the sample twice by using the methanol (2mL × 2), pouring the sample into the volumetric flask, transferring 0.1mL of toluene serving as an internal standard substance by using a transfer pipette, adding the methanol for dissolving, uniformly shaking and standing.
The presence of the photoinitiator was observed using Shimadzu LC-20A liquid chromatography (shim column, 150 × 6.0.0 nm, detector SPD-20A, limit of detection 20ppm, detection wavelength 254nm) at 25 ℃ using a flow rate of 1.0mL/min, mobile phase (volume ratio methanol/water 90/10), indicating greater mobility as the initiator content in the liquid phase is higher in percentage of the area of the liquid phase peak to toluene.
(4) Determination of surface dryness
The method of blowing cotton balls (GB/T1728-1979 (1989)) is adopted, and 1 piece of the film is lightly placed on the surface of the cured film for 1cm2The cotton ball is lightly blown with a nozzle 15cm away from the cotton ball in the horizontal direction.
If the cotton ball can be blown away, no cotton silk is left on the surface of the film, which is marked as A;
if the cotton ball can be blown away, but cotton threads are left on the surface of the film, which is marked as B;
if the cotton ball can not be blown away, the mark is C;
if the cotton balls can be blown away, no cotton silk is left on the surface of the film, namely the surface is dry, which shows that the surface drying performance of the film is excellent.
The characterization results are shown in table 3.
TABLE 3
Figure BDA0001520771200000211
As can be seen from the test results in Table 3, the fluorene oxime ester photoinitiator containing polymerizable groups shown in the general formula (I) has excellent surface drying performance, high initiator efficiency and high curing speed in photocuring application, does not migrate, and has obviously better comprehensive performance than the existing oxime ester photoinitiator products.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. The fluorine-containing fluorene oxime ester photoinitiator is characterized by having a structure shown in a general formula (I):
Figure FDA0002445796770000011
wherein n represents an integer of 1 to 4; m represents an integer of 1 to 4;
n of said R1Each independently selected from-G- (M') q, hydrogen, nitro, halogen, or
Figure FDA0002445796770000012
m' represents an integer of 1 to 4; wherein G is selected from a heteroatom or a carbonyl group, the heteroatom is O, N or S, and M' is selected from C1～C20Straight or branched alkyl of (2), C3～C8Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)6～C20Aryl, nitro substituted C of6～C20Aryl, cyano-substituted C6～C20Aryl radical, C4～C20Heteroaryl, nitro substituted C of6～C20Heteroaryl or cyano-substituted C6～C20Heteroaryl, or one or more carbon atoms of said M' are substituted by said heteroatom, q is 1 or 2;
the R is2And said R2' each is independently selected from polymerizable groups;
said Z and said Z' each independently represent a null or a carbonyl group;
m of said R3And m' said R5Each independently selected from fluorine, linear or branched alkyl substituted by one or more fluorine, linear or branched alkoxy substituted by one or more fluorine;
the R is4And said R6Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C1～C10Alkyl radical, C1～C10Alkyl-substituted C of3～C8Cycloalkyl radical, C6～C20Aryl of (C)4～C20Heteroaryl or C of2～C20Alkenyl groups of (a).
2. The fluorofluorenyloxime ester photoinitiator as claimed in claim 1, wherein M is selected from the group consisting of’Is selected from C1～C10Straight or branched alkyl of (2), C3～C6Cycloalkyl of, C3～C6Cycloalkyl-substituted C of1～C5Alkyl of (C)6～C10Aryl, nitro substituted C of6～C10Aryl, cyano-substituted C6～C10Aryl radical, C4～C10Heteroaryl, nitro substituted C of6～C10Heteroaryl or cyano-substituted C6～C10Heteroaryl radical。
3. The fluorofluorenyloxime ester photoinitiator as claimed in claim 1, wherein R is selected from the group consisting of2And said R2' are each independently selected from polymerizable groups containing a double bond or an epoxy group.
4. The fluorofluorenyloxime ester photoinitiator as claimed in claim 3, wherein R is selected from the group consisting of2And said R2' each is independently selected from C2～C12Or said R is2And said R2' one or more of-CH2Each independently of the others by-O-),
Figure FDA0002445796770000021
And (4) substituting.
5. The fluorofluorenyloxime ester photoinitiator as claimed in claim 4, wherein R is selected from the group consisting of2And said R2' each is independently selected from C3～C8Or said R is2And said R2' one or more of-CH2Each independently of the others by-O-),
Figure FDA0002445796770000022
And (4) substituting.
6. The fluorofluorenyloxime ester photoinitiator according to any one of claims 3 to 5, wherein R is R2And said R2' each is independently selected from the group consisting of ethylene oxide substituted C1～C10Alkyl or propylene oxide substituted C1～C10Alkyl, or said R2And said R2' middle C1～C10One or more-CH's in alkyl2Each independently of the others by-O-),
Figure FDA0002445796770000023
Figure FDA0002445796770000024
or-O-CH2-CH(OH)-CH2-O-substitution.
7. The fluorofluorenyloxime ester photoinitiator as claimed in claim 6, wherein R is selected from the group consisting of2And said R2' independently selected from C with ethylene oxide or propylene oxide as end capping group1～C8Or said R is2And said R2' middle C1～C8One or more-CH in alkyl group of (2)2Each independently of the others by-O-),
Figure FDA0002445796770000025
or-O-CH2-CH(OH)-CH2-O-substituted, or H in said ethylene oxide or said propylene oxide group is C1～C4Is substituted with an alkyl group.
8. The fluorofluorenyloxime ester photoinitiator according to any one of claims 1 to 5, wherein m of R are3And m' of said R5Are respectively and independently selected from F,
Figure FDA0002445796770000026
Figure FDA0002445796770000031
9. The fluorofluorenyloxime ester photoinitiator according to any one of claims 1 to 5, wherein R is R4And said R6Are each independently selected from C1～C6Straight or branched alkyl of (2), C3～C10Cycloalkyl of, C3～C6Cycloalkyl-substituted C1～C8Alkyl radical, C1～C8Alkyl substituted C3～C6Cycloalkyl radicalsOr C6～C12Aryl group of (1).
10. The fluorofluorenyloxime ester photoinitiator as claimed in claim 9, wherein R is selected from the group consisting of4And said R6Each independently selected from phenyl and C1～C4Straight or branched alkyl of (2), C3～C8Cycloalkyl or C3～C6Cycloalkyl-substituted C1～C4An alkyl group.
11. The fluorofluorenyloxime ester photoinitiator according to any one of claims 1 to 5, wherein the fluorofluorenyloxime ester photoinitiator is selected from
Figure FDA0002445796770000032
Figure FDA0002445796770000041
Figure FDA0002445796770000051
Figure FDA0002445796770000061
Figure FDA0002445796770000071
Figure FDA0002445796770000081
Figure FDA0002445796770000091
Figure FDA0002445796770000092
One or more of the group consisting of.
12. A photocurable composition comprising a photoinitiator comprising a fluorofluorenyloxime ester photoinitiator according to any one of claims 1 to 11.
13. Use of the fluorofluorenyloxime ester photoinitiator according to any one of claims 1 to 11 in the field of photocuring.
CN201711415551.4A 2017-12-22 2017-12-22 Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator Active CN109957046B (en)

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